Silicone fatty esters

ABSTRACT

The invention relates to a series of novel silicone fatty esters. This class of compounds, provide outstanding softening and lubricating when applied to textiles and fibers. The compounds of the present invention are prepared by reacting a the hydroxyl group in a silicone polymer with a fatty carboxylic acid, ester or anhydride.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a series of novel silicone fatty esters which provide outstanding lubrication, and softening when applied to a variety of fiber substrates. The esterification by which the compounds are prepared involves the reaction of a hydroxyl containing silicone polymer, and a fatty acid, ester or anhydride.

2. Arts and Practices

Silicone compounds have been known to be active at the surface of cellulosic and synthetic fibers as well as paper. They are good nondurable lubricants and are very stable to oxidation, however, their high cost and lack of efficiency at low concentrations as well as low durability have made their acceptance in commercial products quite low.

In addition to their high cost, silicone compounds have little or no solubility in mineral oils, fatty triglycerides and other classical fatty quatarnary compounds used for softening. This has resulted in the inability to prepare stable blends for use as a textile fiber treatment.

In many applications, there is a desire for a more fatty soluble softener. The desired molecule should have the desirable softening and antistatic properties of silicone, yet have compatibility with traditional fatty materials and oils. Even though a textile softener which has both the desirable softening and antistatic properties of silicone as well as compatibility with fatty compounds has been a long felt need, it isn't until the compounds of the present invention that such a system has been attained.

U.S. Pat. No. 3,511,699 to Sterman issued May 12, 1970 teaches that epoxy compounds placed in the silicone backbone by hydrosilation can be cured onto certain fibers to give improved substantivity. The substantivity is based upon the reaction of hydroxyl groups on the cellulosic and the epoxy group in the silicone polymer. The resulting bond is a ether linkage and a new hydroxyl group. While a definite improvement over other compounds the efficiency and durability of the were not good enough to allow for cost effective incorporation of these materials in detergent formulations.

THE INVENTION OBJECT OF THE INVENTION

It is the object of the present invention to provide novel silicone based fatty ester compounds which are substantive to the surface of a fiber and other textile materials including cellulosic material and have increased solubility in fatty materials including mineral oil, fatty triglycerides and traditional fatty quaternary ammonium compounds. The compounds of the present invention render the lubricity, and hydrophobicity generally seen in silicone compounds, but because they are esterified with fatty groups have greater solubility in hydrocarbon oils as well as fatty materials than the traditional silicone compounds which are insoluble in those materials.

It is another objective of the current invention to provide silicone fatty esters which can be used in textile, formulations to render softness and lubrication to the substrates being treated. The superior antistatic properties are an important benefit, since this is a major aspect of consumer perception of softness in consumer and industrial laundry applications. Application of the compounds of the invention can be from solvent, aqueous dispersion or solution, or applied neat in these processes.

SUMMARY OF THE INVENTION

The present invention relates to novel silicone fatty ester compounds. The compounds by virtue of the fatty ester group are soluble in fatty and hydrocarbon products, but have many of the functional softening and lubrication properties of silicone. This property makes these materials excellent additives for highly effective surface modifying finishes for fiber and textiles. The compounds of the present invention are substantive to cellulosic and synthetic fibers as well as metal surfaces and plastic polymers.

The compounds of this invention are silicone fatty esters made by the esterification of a fatty acid, ester, or anhydride and a hydroxy containing silicone compound. The compounds of the present invention conform to the following structure; ##STR1## wherein; R is alkyl having 1 to 20 carbon units;

R¹ is selected from lower alkyl CH₃ (CH)n-- or phenyl;

n is an integer from 0 to 8;

a, b and c are integers independently ranging from 0 to 20;

EO is an ethylene oxide residue --(CH₂ CH₂ --O)--;

PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--;

o is an integer ranging from 1 to 100;

q is an integer ranging from 0 to 500.

In a preferred embodiment, R is CH₃ --(CH₂)₁₆ -- and is derived from stearic acid.

EXAMPLES

The compounds of the present invention are prepared by the reaction of a hydroxy silicone compound and a fatty acid. Examples of suitable reactants are as follows;

    ______________________________________                                         Reactants                                                                      Fatty Acids                                                                               Formula        Molecular Weight                                     ______________________________________                                         Lauric     C.sub.12 (Saturated)                                                                          200                                                  Myristic   C.sub.14 (Saturated)                                                                          228                                                  Stearic    C.sub.18 (Saturated)                                                                          284                                                  Oleic      C.sub.18 (monounsaturated)                                                                    282                                                  Linoleic   C.sub.18 (diunsaturated)                                                                      280                                                  ______________________________________                                    

Hydroxy Silicone Compounds

Union Carbide Chemicals and Plastics, Danbury, Conn., offers a series of hydroxy silicone compounds suitable for use as raw materials in the preparation of the esters of the present invention. These materials are marketed under the SILWET trade name.

The preferred method of placing this type of reactive hydroxyl group into the silicone polymer is by the reaction of silanic hydrogen containing polymer with allyl alcohol alkoxylates. This technology is well known to those skilled in the art and are described in U.S. Pat. No. 4,083,856. These hydroxyl functional silicone compounds are subsequently esterified, by reaction with fatty acids, esters or anhydrides, to make the compounds of the present invention.

Additionally, hydroxy silicone compounds are available from Siltech Inc. Norcorss, Ga. These compounds conform to the following generic structure;

    __________________________________________________________________________      ##STR2##                                                                      Name      a    b     c    o     q                                              __________________________________________________________________________     Siltech H 1000                                                                           3    0     0    2     54                                             Siltech H 1100                                                                           10   5     10   10    100                                            Siltech H 1200                                                                           20   20    20   2     56                                             Siltech H 1300                                                                           10   10    10   6     26                                             Siltech H 1400                                                                           0    10    0    4     200                                            Siltech H 1500                                                                           5    5     5    2     50                                             Siltech H 1600                                                                           0    6     0    10    25                                             Siltech H 1700                                                                           0    0     0    5     10                                             __________________________________________________________________________

General Reaction Conditions

The esterification can be carried out without catalyst; however, when no catalysts are used reaction rates are less efficient. Standard esterification catalysts are generally used at concentrations of between 0.05% to 0.50% with a preferred range of 0.1% to 0.3%. Catalysts which are effective include but are not limited to; sulfuric acid, p-toluene sulfonic acid, methane sulfonic acid, tin metal, zinc metal, titanium metal, organo titianates, organo tin compounds, organo zinc compounds, zinc oxide, magnesium oxide, calcium oxide, etc. The most preferred catalyst is stannous oxylate. The reaction is conducted at between 140 and 240 C. under an inert nitrogen blanket. The nitrogen blanket preserves the color. Preferred temperature range is between 180 and 210 C. Water is removed from the reaction which is done using a nitrogen sparge or vacuum.

The reaction can be run with either a stiochiometric amount of the fatty acid, or a slight excess of either reactant.

EXAMPLES EXAMPLE 1

Into a suitable round bottom, three neck flask equipped with a Dean Stark trap, a thermometer and a nitrogen sparge is added 284.0 grams of stearic acid, 0.25% by weight of the total batch charged of stannous oxylate and 2,39 grams of Siltech H 1000. The reaction mass is blanketed with nitrogen, and heated to 180 and 200 C. under an inert nitrogen blanket. Once the reaction temperature reaches 120 C. water begins to boil off and is collected in the Dean Stark Trap. Within four to five hours the theoretical water is collected off and the acid value is very low. The product is a clear liquid and is used without additional purification.

EXAMPLES 2-40

Example 1 is repeated only this time substituting the specified number of grams of the fatty acid specified for the stearic acid and the specified type and number of grams of silicone compound as shown below:

    ______________________________________                                                 Fatty Acid  Silicone Compound                                          Example   Type      Grams   Type       Grams                                   ______________________________________                                         2         Lauric    200.0   Siltech 1000                                                                              2,329.0                                 3         Myristic  228.0   Siltech 1000                                                                              2,239.0                                 4         Oleic     282.0   Siltech 1000                                                                              2,239.0                                 5         Caprylic  145.0   Siltech 1000                                                                              2,239.0                                 6         Stearic   284.0   Siltech 1100                                                                              2,032.0                                 7         Lauric    200.0   Siltech 1100                                                                              2,032.0                                 8         Myristic  228.0   Siltech 1100                                                                              2,032.0                                 9         Oleic     282.0   Siltech 1100                                                                              2,032.0                                 10        Caprylic  145.0   Siltech 1100                                                                              2,032.0                                 11        Stearic   284.0   Siltech 1200                                                                              5,129.0                                 12        Lauric    200.0   Siltech 1200                                                                              5,129.0                                 13        Myristic  228.0   Siltech 1200                                                                              5,129.0                                 14        Oleic     282.0   Siltech 1200                                                                              5,129.0                                 15        Capyrlic  145.0   Siltech 1200                                                                              5,129.0                                 16        Stearic   284.0   Siltech 1300                                                                              347.6                                   17        Lauric    200.0   Siltech 1300                                                                              347.6                                   18        Myristic  228.0   Siltech 1300                                                                              347.6                                   19        Oleic     282.0   Siltech 1300                                                                              347.6                                   20        Caprylic  145.0   Siltech 1300                                                                              347.6                                   21        Stearic   284.0   Siltech 1400                                                                              4,407.0                                 22        Lauric    200.0   Siltech 1400                                                                              4,407.0                                 23        Myristic  228.0   Siltech 1400                                                                              4,407.0                                 24        Oleic     282.0   Siltech 1400                                                                              4,407.0                                 25        Caprylic  145.0   Siltech 1400                                                                              4,407.0                                 26        Stearic   284.0   Siltech 1500                                                                              2,783.0                                 27        Lauric    200.0   Siltech 1500                                                                              2,783.0                                 28        Myristic  228.0   Siltech 1500                                                                              2,783.0                                 29        Oleic     282.0   Siltech 1500                                                                              2,783.0                                 30        Caprylic  145.0   Siltech 1500                                                                              2,783.0                                 31        Stearic   284.0   Siltech 1600                                                                              3,550.8                                 32        Lauric    200.0   Siltech 1600                                                                              3,550.8                                 33        Myristic  228.0   Siltech 1600                                                                              3,550.8                                 34        Oleic     282.0   Siltech 1600                                                                              3,550.8                                 35        Capyrlic  145.0   Siltech 1600                                                                              3,550.8                                 36        Stearic   284.0   Siltech 1700                                                                              1,512.4                                 37        Lauric    200.0   Siltech 1700                                                                              1,512.4                                 38        Myristic  228.0   Siltech 1700                                                                              1,512.4                                 39        Oleic     282.0   Siltech 1700                                                                              1,512.4                                 40        Caprylic  145.0   Siltech 1700                                                                              1,512.4                                 ______________________________________                                    

APPLICATIONS EXAMPLES Applications of the Compounds of the Invention

Compounds of this invention were compared to standard compounds commercially available using AATCC Test Method 117-1979. The color fastness heat test uses a 400 F. (205 F.) hot iron which is applied for 60 and 180 seconds. The color is rated on a 1-5 basis for yellowness, (5 being the most yellow).

    ______________________________________                                         Compound              Yellowness                                               ______________________________________                                         Alkaquat T (Imidazoline Quat)                                                                        4                                                        Alkaquat DAET 90 (Amido Quat)                                                                        5                                                        Example #1            1                                                        Example #6            2                                                        Example #36           2                                                        Example #26           1                                                        Example #15           2                                                        Siltech H 1100        4                                                        ______________________________________                                    

As can be seen the compounds of the present invention are non-yellowing softeners when compared to standard softeners.

LUBRICATION Frictional Properties

    ______________________________________                                         LUBRICATION DATA.sup.1                                                         Coefficient of Friction                                                                                   FIBER/METAL                                                      DESCRIPTION   100 300                                             PRODUCT      (70 F)        (m/min.)                                            ______________________________________                                         Butyl Stearate                                                                              White Liquid  0.17 0.21                                           Tridecyl Stearate                                                                           Clear Liquid  0.25 0.27                                           Example 6    Clear liquid  0.10 0.11                                           Example 16   Clear Liquid  0.07 0.09                                           Example 19   Clear liquid  0.06 0.02                                           Example 12   Clear Liquid  0.09 0.04                                           Ditallowdimethyl                                                                            Tan solid     0.35 0.35                                           benzalkonium chloride                                                          Ditridecyl adipate                                                                          Clear Amber Liquid                                                                           0.28 0.29                                           Untreated Fiber            0.98 1.01                                           ______________________________________                                          .sup.1 Rothchild F Meter, Fiber; 150 denier polyester, Temperature; 72 F,      Relative humditiy; 60%                                                   

As can be easily seen the compounds of the present invention are excellent lubricants. 

What is claimed:
 1. A silicone ester which conforms to the following structure: ##STR3## wherein: R is alkyl having 11 to 20 carbon units;R¹ is selected from lower alkyl or phenyl; a, b and c are integers independently ranging from 0 to 20; EO is an ethylene oxide residue --(CH₂ CH₂ --O)--; PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--; o is an integer ranging from 1 to 100; q is an integer ranging from 0 to
 500. 2. A compound of claim 1 wherein R¹ is lower alkyl.
 3. A compound of claim 1 wherein R¹ is CH₃.
 4. A compound of claim 1 wherein R¹ is phenyl.
 5. A compound of claim 1 wherein a+b+c=0.
 6. A compound of claim 1 wherein a, b and c are independently integers between 2 and
 10. 7. A compound of claim 1 wherein R is CH₃ --(CH₂)₁₆ --.
 8. A compound of claim 1 wherein R is CH₃ --(CH₂)₁₄ --.
 9. A compound of claim 1 wherein R is CH₃ --(CH₂)₁₂ --.
 10. A compound of claim 1 wherein R is CH₃ --(CH₂)₁₀ --.
 11. A silicone fatty ester compound which is prepared by the esterification of a fatty acid, having 11 to 20 carbon atoms with a hydroxy silicone compound conforming to the following structure; ##STR4## wherein: R is alkyl having 11 to 20 carbon units;R¹ is selected from lower alkyl or phenyl; a, b and c are integers independently ranging from 0 to 20; EO is an ethylene oxide residue --(CH₂ CH₂ --O)--; PO is a propylene oxide residue --(CH₂ CH(CH₃)--O)--; o is an integer ranging from 1 to 100; q is an integer ranging from 0 to
 500. 12. A compound of claim 11 wherein R is CH₃ --(CH₂)₁₆ --.
 13. A compound of claim 11 wherein R is CH₃ --(CH₂)₁₄ --.
 14. A compound of claim 11 wherein R is CH₃ --(CH₂)₁₂ --.
 15. A compound of claim 11 wherein R is CH₃ --(CH₂)₁₀ --. 